DE2801219A1 - METHOD OF POLYMERIZING VINYL MONOMERS - Google Patents

Description

JABGER, GRAMS & PONTANI> 8Ö 12

PATENT LAWYERS "~ DlPLCHEM. DR. KLAUS JAEGER DIPL.-ING. KLAUS D. GRAMS DR.-ING. HANS H. PONTANI GAUTING ■ BERGSTR. 48Vi BO31 STOCKDORF · KREUZWEG 34 8762 KLEINOSTHEIM · HIRSCHPFAD

SHI-18-

Shin-Etsu Chemical Co., Ltd.

0-1, Otemachi 2-chome, Chiyoda-ku, Tokyo, Japan

Process for polymerizing vinyl monomers

The invention relates to a method of polymerizing of vinyl monomers, in which the polymerization is carried out m a polymerization reactor, whose is surfaces in contact with vinyl monomers prior to charging the reactor with the starting component mixture to be polymerized with one or a mixture several polar organic substances are wet coated and then dried.

"Vinyl monomers" for the purposes of the invention are both pure Substances such as vinyl chloride or styrene, as well as mixtures of such substances such as a mixture of vinyl chloride and vinylidene chloride, as well as a mixture of pure vinyl monomers or a mixture of vinyl monomers with other copolymerizable monomers

TELEPHONE; (O8Ü) ΒϋΟ2Ο3Ο; 8ä74OÜO; (OSO27) 8825 · TELEX: 521 777 isar d

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such as a mixture of styrene and butadiene.

“Polymerization reactor” or “reactor” for short in the sense of the description is any type of polymerization tank or Polymerization vessel in which such polymerizations of vinyl monomers are usually carried out in the presence of a polymerization initiator be performed. Those in contact with the vinyl monomers of the starting component mixture The surfaces of the polymerization reactor that reach it are mainly its inner surfaces of the vessel walls, but also surfaces of fittings and device parts, for example the surface of a stirrer, as far as they are with comes into contact with the vinyl monomers. Such surfaces are also shown below for the sake of clarity under the term "reactor surface" or "surface" for short as used below.

That which occurs specifically in the polymerization of vinyl monomers in polymerization reactors of the type mentioned The problem is the formation of polymer incrustations on the surfaces that come into contact with the monomers. Such incrustations occur in all processes customary for the polymerization of vinyl monomers for example in suspension polymerisation as well as in emulsion polymerisation, polymerisation from solutions and bulk polymerization.

The formation of the polymer incrustations leads to a decrease in the polymer yield the cooling capacity of the reactor and flaking of parts of the incrustation leads to a deterioration in quality of the product polymer. In addition, the incrustation must occur after each polymerization batch or polymerization run removed. This removal of the incrustation is an inefficient use of manpower and decreases the productivity of the polymerization plant. In addition, the polymer incrustations require

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a common one for cleaning and checking purposes Entering the reactors. It has recently been found that the remains of the in the crusts retained volatile vinyl monomers pose a serious health hazard to those entering the reactor Represent person.

It is known from US Pat. No. 3,669,946 for suppression the polymer encrustation of the reactor surfaces which come into contact with the vinyl monomers these surfaces to be coated with polar organic substances before the start of the polymerization reaction. As coating substances are organic dyes, amines, quinones and aldehydes.

The disadvantage of this process, which is actually quite effective, is the requirement to use organic solvents when making the paintings. This leads to safety problems and health problems in industrial practice. The attempt to use the organic solvent in the paints known from US Pat. No. 3,669 Replacing it with water leads to useless results. The formation of the polymer crusts on the reactor surfaces is practically no longer reduced when using such aqueous paint systems.

Another disadvantage of this known coating process is that it is not suitable for all polymerization reaction systems is equally effective. So are even the protection claims made using organic solvents when carrying out emulsion polymerizations or when carrying out polymerizations in the presence an emulsifier practically completely ineffective, while the same paints are in the aqueous suspension polymerization vinyl chloride, styrene and a mixture of these monomers have proven to be quite effective.

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For the polymerization of vinyl chloride are commonly used Stainless steel reactors used. This is known for the emulsion polymerization of styrene and for the copolymerization of styrene and butadiene or acrylonitrile, styrene and butadiene or similar systems not possible because of the unusually strong formation of polymer crusts on the reactor walls. These polymerizations are therefore still usually carried out in internally glazed polymerization reactors, Although the inner glaze worsens the heat transfer coefficient, the service life of the reactor is shortened and the manufacturing cost of the reactors, particularly for large capacity reactors, is substantial elevated.

While the process known from US Pat. No. 3,669,946 for the suspension polymerization of vinyl chloride is too good gives good results, it is ineffective in the emulsion polymerization of styrene or styrene-containing substances Monomer mixtures.

The coating of the polymerization reactor walls which come into contact with the monomers is also known from BE-PSs 837 056, 844 215 and 845 168. According to these known processes, the reactor surfaces also coated with polar organic compounds, namely with an organic dye or a specific combination of two different polar organic compounds, this mixture being optional a metal salt can be added. The surfaces coated with such substances are after coating if necessary treated with an oxidizing agent or a reducing agent.

According to the processes known from the BE-PSs mentioned, the coating materials are likewise in organic solutions

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means dissolved or suspended. applied, whereby as Solvent methyl alcohol, ethyl alcohol, toluene, methylene chloride or dimethylformamide are used. Also at These methods must therefore use organic solvents that have the above-mentioned disadvantages entail. Even if the paints produced according to the BE-PSs effectively suppress incrustation is the type of handling, in particular the type of application of the paints for modern industrial practice not up to date anymore. Even with these protective paints known from the BE-PSs, the Replacement of the organic solvents with water. As comparative examples in the cited publications show, the use of water after drying gives a paint that prevents the formation of polymer incrustations unable to suppress or only insufficiently.

The invention is therefore based on a prior art, according to which it is in connection with the polymerization of Vinyl monomers, especially vinyl chloride, is known, the reactor surfaces coming into contact with the monomers to suppress the deposition of polymer incrustations with an organic solution of polar organic To paint substances such as organic dyes in particular. Despite known attempts In this direction, there is no known aqueous layering liquid that would cause the deposition of the polymer crusts able to suppress with at least the same efficiency as the paints based on organic solvents.

The aim of the invention is to create improved processes for polymerizing vinyl monomers, specifically improving these processes in their prior to the actual chemical polymerization reaction

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stages in which the reactor surfaces come into contact with the monomers during the polymerization reaction be covered with a coating that causes a deposition of polymer crusts on these surfaces should suppress. The invention is intended to achieve the use of organic substances required by the prior art Avoid solvents in the manufacture of the coatings on the reactor surfaces and from aqueous liquids enable the production of coatings which the polymer encrustation with at least the same Able to suppress effectiveness such as the coatings produced using organic solvents, the result compared to the known attempts to produce aqueous coating liquids to product Lead polymerizaten that do not contain any crust flakes included and thus of improved quality and which ultimately have the same good effectiveness in suppressing polymer incrustations in the polymerization reactor effect uniformly for all types of polymerization reactions, i.e. both for suspension polymerization as well as emulsion polymerization or bulk polymerization as well as for homopolymerizations or Copolymerizations used with the same effectiveness who can, regardless of the type of used Polymerization initiators and the other, the polymerization starting component mixtures usually added additives.

The invention is based on the technical problem for the above-mentioned process for polymerizing Vinyl monomers, especially for its precursor, in which the reactor surfaces that come into contact with the vinyl monomers coated with polar organic substances, an aqueous coating liquid create, using which, by simply drying the paint applied to the surfaces, water-resistant

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soluble or converted into the water-insoluble form coatings are obtained, which in the subsequent Carrying out the actual polymerization reaction in the reactor, the formation and deposition of polymer crusts prevent on these surfaces, regardless of the polymerization reaction parameters and composition of the reaction mixtures.

The failure of the known attempts aimed in this direction may be seen in the difficulty in finding water-insoluble Produce paints from aqueous dispersions or solutions by simply drying the application.

To solve this problem, a method of the initially mentioned type proposed, which is characterized according to the invention in that the polymerization in a polymerization reactor is carried out in which the coating with the polymerization starting component mixture surfaces coming into contact with an aqueous coating liquid is made, which at least an alkali metal salt or an ammonium salt of a water-soluble sulfonic acid type anionic dye or of the carboxylic acid type and with the addition of a pH-influencing reagent to a pH of is set to no greater than 7.

The process characterized in this way is able to suppress the deposition of polymer crusts to a surprising extent. This effect occurs on all types of surfaces that come into contact with the monomers, i.e. both on the inner wall surfaces of the reactor housing itself and on the surfaces of stirrer blades, Stirrer bars or stirrer shafts as well as on other parts of fittings, for example thermometer sleeves. The effect is also both qualitatively and quantitatively independent of the type of polymerization,

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is therefore independent of whether the polymerization is a suspension polymerization, Emulsion polymerisation or bulk polymerisation is carried out - neither will it by the specific nature of the polymerized vinyl monomers and the composition of that which has undergone the polymerization Starting component mixture influenced. The formation and deposition of the Polymerisatiinkrustationen is also both on steel reactor surfaces and on the surfaces of glazed or enameled polymerization reactors causes. The real advantage of the invention, however, is that the coating with of the aqueous coating liquid polymerization reactors made of simple stainless steel also for all those polymerizations can be used for which they have hitherto also been based on the use of the known paints organic solvent base could not be used because, despite the paint according to the prior art, it was too strong Polymer encrustation order. The use of the aqueous coating liquid also increases the safety risks and health risks associated with handling paints based on organic solvents are avoided are inevitably connected. Avoiding the use of organic solvents in the coating liquid is also reflected positively in the cost of the coating. Also the flammability of the known Coating liquids and the risk of explosion when producing the coatings are due to the use of the aqueous coating liquids is eliminated.

The high effectiveness of the suppression of the formation of polymer incrustations which can be achieved by the invention is probably due to a particularly strong adhesion caused by drying the wet coating on the surfaces obtained coating layer on the substrate, which in turn is probably due to the good water-

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insolubility or very low solubility in water of the film-forming substances is due to their Starting components are present in the coating liquid. The essentially water-insoluble ones formed in this way and coatings which adhere extremely firmly to the reactor surfaces have an extraordinarily high quality high adhesion repellency / are able to adsorb polymerization products to an unusually high degree to suppress on the walls. The basis for this phenomenon is not yet sufficient clarified. What is surprising, however, is the observation that this adsorption rejection affects both the dissociated as well as acts on the undissociated particles in the polymerization mixture, regardless of the phase relationships in the Polymerization system.

In the following, as examples of the sulfonic acid type and carboxylic acid type anionic dyes, the are used in the form of their alkali metal salts or their ammonium salt, preferably used representatives compiled. In order not to make the composition of these preferably used dyes more difficult to read, instead of their full chemical names, their designations are given according to the "Color Index" ("CI" for short). The "Color Index" is published and fulfilled by the English "Society of dyers and colourists" in the international professional world, it functions as an unofficial reference standard. Even for the non-specialist In other words, the chemical composition of the dyes named below according to this Color Index are clear identifiable.

(1) Sulphonic acid type dyes:

C.I. Acid yellow 38, C.I. Food Yellow 3, C.I. Reactive Yellow 3, C.I. Direct orange 2, C.I. Direct Orange 10,

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Acid red 18, C.I. Acid Red 52, C.I. Acid red 73, C.I. Direct Red 186, CI. Direct red 92, C.I. Direct violet 1, C.I. Direct Violet 22, CI. Acid Violet 11, C.I. acid ViöLet 78, CI. Mordant Violet 5, C.I. Direct blue 6, C.I. Direct Blue 71, C.I. Direct blue 106, C.I. Reactive Blue 2, CI. Reactive Blue 4, CI. Reactive Blue 18, C.I. Acid Blue 116, CI. Acid Blue 158, CI. Acid Black 1, C.I. Acid black 2, C.I. Direct Black 38, CI. Solubilized Vat Black 1, CI. Fluorescent Brightening Agent 30, CI. Fluorescent Brigntening Agent 32, C.I. Acid Blue 1, CI. Acid Blue 40, CI. Acid blue 59, C.I. Acid Blue 113, C.I. Acid Orange 7, C.I. Direct blue 1, C.I. Direct Blue 86, CI. Direct Orange 26, CI. Direct red 31, C.I. Direct Black 19, C.I. Direct black 32, C.I. Direct Black 77, CI. Direct Green 1, C.I. Acid orange 3, C.I. Acid black 124, C.I. Acid Red 52, C.I. Acid Red 80.

(2) Carboxylic acid type dyes and dyes containing both sulfonic acid groups and carboxylic acid groups wear:

CI. Direct Yellow 1, CI. Direct Red 1, CI. Mordant Black 5, CI. Azoic Brown 2, CI. Direct Brown 1, C.I. Direct Brown 101, CI. Direct Green 26, CI. Acid Red 87, C.I. Mordant Yellow 26, C.I. Direct Brown 37 and C.I. Direct Orange 97.

Those in the form of their alkali metal salts or their ammonium salt anionic dyes used, for the representatives typical and preferably used above are named are briefly referred to below as "component a".

Aqueous solutions of component a have relatively low concentrations of the order of 0.1 to 1% by weight has a pH of about 10. With such

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alkaline aqueous solutions of component a can when applying the solution to the realtor surfaces no noticeable effects in terms of oppression the formation and deposition of polymer crusts achieved will. It is crucial for the success of the invention that the pH of the aqueous solution of component a a value not greater than 7, preferably not greater is set as about 5. This pH adjustment is carried out by adding a pH adjusting agent to the Solution.

Such pH adjusting agents for adjusting the pH of the aqueous dispersion or the aqueous solution of the Component a is in particular a wide variety of organic and inorganic acids such as sulfuric acid, Hydrochloric acid, phosphoric acid, nitric acid, carbonic acid, perchloric acid, molybdic acid, tungstic acid, formic acid, Acetic acid, oxalic acid, lactic acid, maleic acid, glycolic acid, thioglycolic acid and phytic acid as well as their acidic salts, insofar as these acids form acidic salts. Of the above substances, preferred are Sulfuric acid, phosphoric acid, nitric acid, molybdic acid, lactic acid, glycolic acid, thioglycolic acid and Phytic acid and, as far as they are formed, their acidic salts are used. With these preferably used Substances will give better results in suppressing polymer incrustation. The aforementioned pH adjusters are preferably used in the form of their aqueous solutions.

The ones that come into contact with the vinyl monomers Aqueous coating liquid to be applied to reactor surfaces is prepared in such a way that component a is first dissolved in water or is dispersed and the solution or dispersion thus obtained is added the pH adjusting agent in an amount

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becomes that the pH of the resulting aqueous liquid is about 7 or below. The concentration of component a in the coating liquid is preferably in the range of about 0.01 to about 5% by weight. In the individual case, the concentration to be chosen as the optimum depends on the solubility of the Component a in water, the processability of the coating liquid obtained when the coating is applied and the decrease in the solubility of component a in water when the pH is lowered to a value of less than 7.

The aqueous coating liquid thus prepared with a pH of 7 or less is applied to the reactor surfaces in the sense defined above and dried to form the polymer incrustation deposition suppressive coating. The workability, especially the applicability and that The coating liquid will run on the surface to be painted by adding a small Amount of a monohydric alcohol with three to 5 carbon atoms in the molecule improved. The alcohol will preferably added in an amount of 1 to 20% by weight. Monohydric alcohols of the type mentioned are for example n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, Isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, η-amyl alcohol, tert-amyl alcohol, isoamyl alcohol and sec-amyl alcohol. Of the alcohols mentioned is Isobutyl alcohol is preferred because it smells the most pleasant.

The addition of the monohydric alcohol to the coating liquid not only improves the workability when applying the coating liquid, but surprisingly also affects the suppression the formation and deposition of polymer crusts

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positive.

It is not recommended to use methanol or ethanol as to use monohydric alcohol. In order to achieve the desired results, larger amounts of these alcohols must be used Quantities are added than that of the higher monohydric alcohols. Monohydric alcohols with more than 5 Carbon atoms already have a noticeably lower solubility in water and are for this reason than Addition less suitable.

According to a further development of the invention, the desired effect can be achieved qualitatively and quantitatively by the Addition of a water-soluble cationic dye ("component b") can be improved, its molecule at least contains a pair of conjugated double bonds and preferably contains at least one nitrogen atom.

According to another development of the invention, the coating liquid can in addition to component a or to components a and b as component c a water-soluble silica, a water-soluble silicate and / or the water-soluble salt of a metal other than alkali metal is added.

The addition of component b to the coating liquid reduces the amount of coating material required for coating and lowers the amount of coating required for drying The minimum temperature that must be applied in order to achieve sufficiently durable coating layers with full Effectiveness in suppressing the deposition of polymer scale form. By adding component c The durability and the service life of the coatings on the reactor surfaces become the coating liquid improved.

As water-soluble cationic dyes are used for

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Component b preferably uses the following substances: water-soluble azine dyes such as CI. Basic Red 2, CI. Basic Blue 16 or CI. Basic black 2; water-soluble acridine dyes such as CI. Basic Orange 14 or CI. Basic Orange 15; water-soluble triphenylmethane dyes such as dyes such as CI. Basic Blue 1, CI. Basic Violet 3, CI. Basic Blue 26, CI. Basic Violet 14, CI. Basic Blue 5 or CI. basic Blue 7; water-soluble thiazine dyes such as CI. Basic Blue 9, CI. Basic Yellow 1, CI. Basic Blue 24, CI. Basic Blue 25 or CI. Basic Green 5; water-soluble polymethine dyes such as CI. Basic Red or CI. Basic Yellow 11; water-soluble diphenylmethane dyes such as CI. Basic Yellow 2; water-soluble xanthene dyes such as CI. Basic Violet 10 or CI. Basic Red 1; water-soluble azo dyes such as CI. Basic Orange 2 or CI. Basic Brown 1; and water-soluble oxazine dyes such as CI. Basic Blue 12 or CI. Basic blue

The following substances are preferably used as component c: water-soluble silicas or silicates such as for example orthosilicic acid, metasilicic acid, orthodisilicic acid, Metatysilicic acid, metatetra silicic acid, sodium metasilicate, sodium orthosilicate, sodium disilicate, Sodium tetrasilicate, potassium metasilicate, potassium hydrogen disilicate, Lithium orthosilicate, hexalithium disilicate, water glass, dodecatungstic acid, decatungstic acid, Potassium Dodecatungsten Silicate, Potassium Decatungsten Silicate, Sodium Dodecatungstosilicate, Molybdosilicic Acids, Potassium Molybdosilicate or sodium molybdosilicate; and water-soluble salts such as salts of oxo acids, acetic acid, Nitric acid, hydroxides and halides of metals other than alkali metals, preferably metals of the alkaline earth metal group, preferably magnesium, calcium and barium, metals of the zinc group, preferably

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Zinc, metals of the aluminum group, preferably aluminum, metals of the fourth main and subgroup of the periodic table of the elements, preferably titanium and tin, metals of the iron group, preferably iron and nickel, metals of the chromium group, preferably chromium and molybdenum, metals of the manganese group, preferably manganese, metals of the copper group, preferably copper and silver, as well as metals of the platinum group, preferably platinum.

When component b or component c is used in combination with component a in the coating liquid is the weight ratio of component b to component a or the weight ratio of the component c for component a preferably in the range from 100: 0.1 to 100: 1000, in particular in the range from 100: 3 to 100: 100. Under these conditions, particularly firmly adhering coatings are obtained on the reactor walls. The total concentration of components b and / or c and component a is in the aqueous coating liquid preferably in the same range as the concentration of component a itself when it is in the coating liquid is present alone, is therefore preferably in the range from 0.01 to 5% by weight.

Even if components b and / or c are used in addition to component a, the pH value of the aqueous Coating liquid must be kept to a value less than at least about 7 under all circumstances. For coatings made with alkaline coating liquids from a pH above 7, for example with a pH of 10, are not sufficient insoluble in water and therefore noticeably dissolve when they come into contact with aqueous media. You can therefore not to suppress the polymer encrustation with the desired effectiveness. Also are the coatings obtained on the surfaces are water-soluble,

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if the components a, b and / or c instead of an aqueous solution in a solution based on organic solvents be applied. The coatings applied from the organic phase peel off if they are used during the Polymerization come into contact with aqueous systems. This leads to a relatively rapid formation of the polymer crusts .

One possible mechanism for the formation of the coating with the surprisingly improved effectiveness in suppression the deposition and formation of polymer crusts in the application according to the invention from acidic aqueous solution is seen in the following:

The water-soluble anionic dye used as component a has at least one group -SO ^ M or -COOM, where M stands for an alkali metal or the ammonium group. These sulfonate or carboxylate groups are in organic ones Solvents undissociated before. In contrast, they dissociate in aqueous solutions and form the following equilibria:

(1) -SO ₃ M ■ _--: ■ -__ ■ ._-- -S0 ~ + M ⁺ (2). -COOM;. --- _ :. r -C00 ~ + M ⁺

By lowering the pH of the solution to a value of 7 or less by adding the pH adjusting agent to the solution in equilibrium, the following new equilibria are set:

(3) -S0 ~ + M ⁺ + H ⁺ ^ z ^ _ · -SO ₃ H + M ⁺

(4) -C00 ~ + M ⁺ + H ⁺ -COOH + M ⁺

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Due to the small amount of only 0.01 to 5% by weight Concentrations of component a in the coating liquid are formed when the solution is acidified to one pH value less than or equal to 7, preferably less than or equal to 5, no precipitates.

When drying the wet applied to the reactor surface Coating from the coating liquid, i.e. when the water is drawn off from the coating liquid, the equilibrium represented by equations 3 and 4 shifts to the right-hand side of the Equations so that there is a water-insoluble or at least practically insoluble in water on the reactor surfaces Forms a coating layer that is unusually dense, unusually strong and likely to adhere to the substrate thereby the unexpectedly good properties in terms of on the suppression of incrustation formation.

To carry out the method of the invention, the entering into contact with the vinyl monomers reactor surfaces are first coated with the aqueous coating liquid or painted and then dried at a temperature in the range of preferably 40 to 100 ⁰ C. Alternatively, the aqueous coating liquid is applied to the surfaces, which have already been heated to a temperature of preferably in the range between 40 and 100 ^{° C.} Whichever method is carried out in detail, it is crucial that the coated surfaces are sufficiently dry before they are washed with water for the first time. After washing with water, which is preferably carried out in between, the actual polymerization reaction can be carried out in a conventional manner known per se in the reactor prepared in this way. The application of the coating compound

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on the reactor surfaces to be protected from incrustation occurs approximately in the amount also provided according to the prior art. Guideline tests have shown that a sufficiently effective prevention of the formation and deposition of polymer crusts on the reactor walls can be obtained if the weight per unit area of the dried coating is only slightly greater than 0.001 g / m ² .

The effectiveness of the process of the invention is not limited to particular types of polymerization. The process of the invention can be used with the greatest success for both suspension polymerization and emulsion polymerization or bulk polymerization. The efficiency of the incrustation suppression is also not influenced by additives which are customarily added to the mixtures to be polymerized. For example, the following substances can be added to the mixtures to be polymerized without any negative effect on incrustation suppression: suspending agents such as, for example, partially saponified polyvinyl alcohol or methyl cellulose; anionic surfactants such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, or sodium dioctylsulfosuccinic acid; nonionic surfactants such as sorbitan monolaurate or polyoxyethylene alkyl ethers; Fillers such as calcium carbonate or titanium dioxide; Stabilizers such as basic lead sulfate, calcium stearate, dibutyltin dilaurate or dioctyltin mercaptide; Lubricants such as rice wax or stearic acid; Plasticizers such as dioctyl phthalate or dibutyl phthalate; Chain transfer agents such as trichlorethylene or mercaptans; Substances for adjusting the pH; Polymerization initiators such as, for example, diisopropyl ^{peroxodicarbonate, α, α 1} -azobis-2,4-dimethylvaleronitrile, lauroyl peroxide, potassium peroxosulfate, cumene hydroperoxide or

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p-menthane hydroperoxide.

The vinyl monomers to be polymerized by the process of the invention are primarily the vinyl halides such as for example vinyl chloride, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acid, methacrylic acid and their esters and salts, maleic acid, fumaric acid and their esters and anhydrides, diene monomers such as, for example Butadiene, chloroprene or isoprene, styrene, acrylonitrile, vinylidene halides and vinyl ethers.

In particular, the method of the invention leads to heterogeneous polymerization in the presence of free radicals gives excellent results in which the formed Product polymer precipitates from the polymerization mixture as the polymerization reaction proceeds. Typical Examples of such polymerizations are the production of homopolymers or copolymers of vinyl halides, Vinylidene halides or a mixture consisting essentially of these two monomers by suspension polymerization or emulsion polymerization in an aqueous medium.

The polymerization process enables unusually good suppression of the formation and deposition of polymer crusts also on the walls of stainless steel polymerization reactors when the polymerization is carried out from styrene, methyl methacrylate or acrylonitrile to fine-grained pearly polymer, in the production of rubber latices such as a styrene-butadiene latex (SBR) or an acrylonitrile-butadiene-latex (NBR) by emulsion polymerization as well as during production of acrylonitrile butadiene styrene resins (ABS).

The invention thus provides a new and improved process for polymerizing vinyl monomers, according to the

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the deposition of polymer crusts on the inner walls of the polymerization reactor and on other surfaces which come into contact with the monomers is suppressed to a considerable extent, which enables the polymers to be produced with significantly improved productivity and significantly improved quality. The vinyl monomers are polymerized in a polymerization reactor, its inner walls as well as all others. Surfaces that come into contact with the monomers have been coated or painted with an aqueous liquid that contains at least one alkali metal salt or an ammonium salt of an anionic dye with sulfonic acid groups and / or carboxylic acid groups in the molecule dissolved or dispersed and whose pH value is added by adding a the pH-adjusting agent has been adjusted to a value of 7 or less, the paint applied wet with such a liquid then being ^{dried at preferably 40 to 100 °} C., so that a water-insoluble or at least practically water-insoluble one appears on the coated surfaces Dye coating forms.

The invention is explained in more detail below on the basis of exemplary embodiments. Those marked with "*" in the tables Tests are blind tests or comparative tests carried out for control purposes.

example 1

The experiments are carried out in a stainless steel polymerization reactor with a capacity of 100 liters, which is equipped with a stirrer also made of stainless steel.

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For making an aqueous coating liquid based on the total weight of the liquid, 1% by weight of C.I. Acid Black 2 dissolved in water. Under use The pH of sulfuric acid is adjusted to the value shown in Table 1 in each case.

The inner walls of the polymerization reactor and the surface of the stirrer (blades and shaft) are coated with the aqueous coating liquid prepared in the specified manner so that the dried coating has a weight per unit area of 0.1 g / m ² . The drying parameters are given in the table. After drying, the coated surfaces are washed with water.

The polymerization reactor pretreated in this way is then charged with 26 kg of monomeric vinyl chloride, 52 kg of deionized water, 26 g of partially saponified polyvinyl alcohol and 8 g of α, α '-azobis-2,4-dimethylvaleronitrile. The polymerization is carried out ^{at 52 °} C. for 8 hours while stirring the polymerization mixture.

After the end of the polymerization, the amount of polymer scale that has settled on the reactor walls is determined for each individual batch. The degree of encrustation is given in Table 1, as in the other tables, as the weight per unit area of the polymer crust in g / m ² .

The test results shown in Table 1 show the influence of the in the coating liquid adjusted pH and the drying conditions (temperature and duration) on the formation of the polymer incrustation refer to. For example, a comparison of tests 5 and 6 shows that an extension of the Drying time from 10 min to 30 min the formation of the

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Able to reduce polymer incrustation from 300 to 200 g / m ^2. It can be concluded from this that insufficient drying of the wet-applied coating leads to unsatisfactory results with regard to the suppression of the formation of the polymer crusts.

Tabel

Vers. Coating no. substance

pH adjustment value

without

Drying incrustation (g / m ² )

1,500

2 C.I.Acid Black 2 yes

5.0

⁰ C

no 1 0.8 RT, 1 0 min no 1 0.8 90 ⁰ C 1 0 min Yes 5.0 RT, 1 0 min Yes 5.0 RT, 30 min

1,200

1,000

300

200

RT = room temperature

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Example 2

The experiments are carried out in a stainless steel polymerization reactor with a capacity of 1,000 liters, which is equipped with a stirrer. The inner surfaces of the reactor walls and the surfaces of the stirring tool which come into contact with the monomers are coated in such a way that the coating obtained has a dry weight of 0.1 g / m ² . The aqueous coating liquid for producing these coatings is an aqueous solution of the anionic dyes listed in Table 2 with a concentration of 1% by weight. The pH of this coating liquid is adjusted in the manner shown in Table 2 to the value also shown in Table 2. The surfaces painted wet with this coating liquid are then dried under the action of heat and then washed thoroughly with water.

The polymerization reactor prepared in this way is charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 40 g of diisopropyl peroxodicarbonate, 250 g of partially saponified polyvinyl alcohol and 25 g of hydroxypropylmethyl cellulose. The polymerization is carried out ^{at a temperature of 57 °} C. for 12 hours while stirring the mixture. After the polymerization reaction has ended, the polymerization mixture is discharged from the reactor, the reactor is washed with water and dried. Finally, the degree of incrustation is determined in the manner described in Example 1.

The results obtained are summarized in Table 2.

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Vers. Coating no. substance

Table 2

pH-one-pH-medium value

Drying

7 * without - - 8 * C.I.Acid Black 2 without 10.8

90 ⁰ C, 10 min

Incrustation (g / m ² )

1 300 1 000

9 * Il sulfur
acid 9.5 11 500 10 * It Il 8.0 11 330 11 Il Il 7.0 II 51 12th Il Il 6.0 Il 15th 13th It Il 5.0 Il 2 14th It It 3.0 Il 2 15th CIDirect
Yellow 1 Oxal
acid 3.5 60 ⁰ C,
30 min 3 16 CIAcid
Black 1 Hydrochloric acid 2.5 II 11 17th CIAcid
Blue 158 6.5 It 12th 18th CIDirect
Blue 6 phosphorus
acid 5.0 Il 2 19th CIDirect
Violet 22 Phytin
acid 5.0 Il 2 20th CIMordant
Violet 5 Saltpetre
acid 3.0 50 ⁰ C,
60 min 5 21st CIDirect
Black 38 molybdenum
acid 4.5 ■ 1 5 22nd CIAcid
Blue 116 Lactic acid 6.5 Il 11 23 CIDirect
Blue 106 Il 6.0 50 ⁰ C,
60 min 8th

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24 CIDirect
BLue 71 Malein
acid 6.0 50
60 ° c,
min 9 25th CIMordant
Blue 1 phosphorus
acid 4.0 40
120 Op
min 4th 26th C.I.Reactive Il 4.5 Il 4th 27 CIAcid
Violet 78 Glycolic
acid 5.0 Il 2 28 CIReactive
Blue 18 Thioglycol
acid 4.0 " 2 29 CIDirect
Orange 2 Oxal
acid 6.0 90
10 W.
min 23 30th CIAcid Red
73 Il 5.5 Il 20th 31 CIDirect
Red 1 vinegar
acid 4.5 Il 20th 32 CIDirect
Violet 1 Il 5.0 Il 16 33 CIMordant
Yellow 26 Il 5.0 Il 13th 34 CIFood
Yellow 3 sulfur
acid 6.5 Il 18th 35 CIAcid
Yellow 38 Il 5.5 Il 12th 36 CIReactive
Blue 4 Il 4.5 Il 10 37 CIDirect
Red 186 Il 3.5 It 8th

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Example 3

The tests are carried out in a stainless steel polymerization reactor with a capacity of 1,000 liters. The polymerization reactor is equipped with a stirrer. The inner walls of the reactor and the surfaces of the stirring tool which come into contact with the monomers are wet coated with an aqueous coating liquid which each contains 1% by weight of the substance listed in Table 3. The coating is carried out in such a way that the dried coating layer has a weight per unit area of 0.1 g / m ² . The wet-applied coating is dried under the conditions shown in Table 3 and then washed with water.

The polymerization reactor pretreated in the manner described is charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water and other additives, but in each case with a polymerization initiator and a dispersant of the type specified in Table 3. Polymerization is carried out for 10 hours at 57 ^° C. with stirring. After this reaction time, the polymerization mixture is discharged from the reactor. The degree of incrustation is determined. The results obtained are shown in Table 3.

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Table 3

Vers. Coating Drying Initiator Dispergator Ver-Nr. liquid crust

as in the attempt

No.

38

39

40

41

42 *

43 *

13 14 18

28

90 ⁰ C,
1 0 min DMVN,
0.075 PVA, 0.25 0 ■ ι KPS,
0.13 Na-LS,
2.5 1 If APS, 0.13
+
0.0013 FeC Na-DBS;
2.5
H 2 Il IPP,
0.075 Na-LS, 2.5
+ Cetyl
alcohol,
2.5 0 Il KPS,
0.13 Na-LS, 1
2.5 600 Il DMVN
0.075 PVA, 0.25 800

Note: DMVN = α, α'-azobis-2,4-dimethylvaleronitrile

KPS = potassium peroxosulfate

APS = ammonium peroxosulphate

IPP = diisopropyl peroxodicarbonate

PVA = partially saponified polyvinyl alcohol

Na-LS = sodium lauryl sulfate

Na-DBS = sodium dodecylbenzenesulfonate

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Example 4

The inner walls that come into contact with the monomers to be polymerized and other surfaces of a combined plant / which consists of an upright 21 stainless steel polymerization reactor and a horizontal 41 stainless steel polymerization reactor are coated with an aqueous coating liquid. The solid concentration in the coating liquid is 1% by weight. The composition of the coating liquid is shown in Table 4. The surfaces are coated in such a way that the dried coating has a weight per unit area of 0.1 g / m ² . The wet applied coating is dried under the conditions given in Table 4, then washed with water and finally subjected to a final drying.

The 21 reactor is charged with 800 g of vinyl chloride monomer and 0.3 g of diisopropyl peroxodicarbonate. It is polymerized with heating at a temperature of 60 ^° C. for 2 hours. It is stirred at a speed of 900 min. After this time, the polymerization mixture is transferred to the 41 reactor, in which a further 800 g of vinyl chloride monomer and 0.4 g of diisopropyl peroxodicarbonate have been placed. The polymerization is carried out for a further 10 hours with heating at a temperature of 57 ^° C., stirring at a speed of 100 min. After the polymerization reaction has ended, the polymerization mixture is discharged. The degree of encrustation on the inner walls of both polymerization reactors is determined. The results obtained are shown in Table 4.

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o 121 e

Table 4

Verse.
No. . Coating
liquid
as in verse.
No. Example 5 Drying Incrustation
(g / m ² ) 800 without - 21 reactor 41 reactor 1 44 * 13th 90 ⁰ C,
1 0 min 900 2 45 27 fl 10 700 46 4th Il 5 47 * 700

The experiments are carried out in an internally glazed polymerization reactor with a capacity of 100 l with a stirrer. The inner walls of the reactor and the stirrer surfaces are coated with a 1% strength by weight aqueous coating liquid which has the detailed composition given in the table. The coating is carried out in such a way that the dried layer has a weight per unit area of 0.1 g / m ² . Following the wet coating is dried 10 min at 90 ⁰ C. Then it is washed thoroughly with water. The polymerization reactor pretreated in this way is charged with 20 kg of vinyl chloride monomer, 40 kg of deionized water, 13 g of potassium peroxosulfate and 250 g of sodium lauryl sulfate. The polymerization is carried out ^{at 50 °} C. for 12 h with stirring. After this time, the polymerization mixture is discharged from the reactor. The incrustation in the reactor is determined. The results obtained are summarized in Table 5.

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Coating
liquid
as in vers. Table 5 Incrustation
(g / m ² ) Verse.
No. without Drying 700 48 * 13th - O 49 14th 9O ⁰ C, 10 min 0 50 4th Il 400 51 * Il

Example 6

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 100 liters. The stirrer and reactor are preheated. The coating liquids specified in Table 6 with a solids concentration of 1% by weight are applied to the heated surfaces of the reactor and stirrer in an amount that the dried coating layer
has a basis weight of 0.1 g / m ² . The wet-applied coating is washed with water after drying.

The polymerization also described in Example 1 is carried out in the polymerization reactor prepared in this way. After completion of the reaction, the reaction mixture is discharged from the reactor and the degree of Definitely encrustation. The results obtained are summarized in Table 6.

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Table 6

Vers. Coating wall and stirrer encrustation no. Liquid temperature
as in verse no.

52 13th 9O ° C 2 53 27 70 ⁰ C 5 54 * 4th 90 ⁰ C 1,000 Example 7

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 400 liters. The stirrer and inner walls of the reactor are coated with a coating liquid, the solids concentration of which is 1% by weight and which otherwise has the compositions shown in Table 7. The coating is applied wet in such a way that the dried paint has a weight per unit area of 0.1 g / m ² . After the wet coating, drying is carried out in the manner indicated in Table 7. The coating is then washed thoroughly with water.

The polymerization reactor pretreated in this way is charged with 200 kg of deionized water, 100 kg of monomeric styrene, 1 kg of calcium phosphate, 10 g of sodium dodecylbenzenesulfonate and 100 g of benzoyl peroxide. It is polymerized with stirring 11h at 90 ⁰ C. After the reaction has ended and the reaction mixture has been discharged, the degree of incrustation is determined. The results are summarized in Table 7.

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_ Ιήλ -

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Coating
liquid like
in vers. Table 7 Incrustation
(g / m ² ) Verse.
No. without Drying 280 55 * 19th - 0 56 28 60 ⁰ C, 30 min 2 57 10 40 ⁰ C, 120 min 200 58 * 90 ⁰ C, 10 min

Example 8

The experiments are carried out in the same reactor in which the experiments of Example 7 were carried out. The inner walls of the reactor and the stirrer surfaces are coated with an aqueous coating liquid, the solids concentration of which is 1% by weight, and which otherwise has the composition specified in Table 8. The dried coating has a weight per unit area of 0.1 g / m ² . After wet painting, it is dried under the conditions shown in Table 8 and then washed with water. The polymerization of styrene is carried out under the conditions mentioned in Example 7. After the completion of the polymerization reaction, the polymerization reaction mixture is discharged from the reactor. The reactor is then washed with water. The reactor is then charged again in the same way and used for a further polymerization batch without the coating being renewed. The amount

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26ÜI213

the loading remains unchanged. This batchwise operation is repeated as often as the incrustation forming on the reactor walls and the stirrer surface does not exceed ^{a weight per unit area of 1 g / m 2.} The results obtained are shown in Table 8.

Coating
liquid like
in vers. Example 9 Table 8. number of
Polymerization
approaches Verse.
No. without
14th
4th Drying 0
13th
0 59 *
60
61 * 90 ⁰ C, 10 min
Il

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 400 liters. The inner walls of the reactor and the surfaces of the stirring tool are coated with an aqueous coating liquid which has a solids concentration of 1% by weight and otherwise has the composition given in Table 9. The coating is applied in such an amount that the dried coating has a weight per unit area of 0.1 g / m ² . After wet painting, drying is carried out with heating in the manner indicated in Table 9 and then washed with water.

The polymerization reactor pretreated in this way is then

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charged with 180 kg of diionized water, 75 kg of 1,3-butadiene monomer, 25 kg of styrene monomer, 4.5 kg of sodium lauryl sulfate, 280 g of tert-dodecyl mercaptan and 300 g of potassium peroxosulfate. The polymerization reaction is carried out ^{at 50 ° C. for 12 h with stirring.} After the polymerization reaction has ended, the reaction mixture is discharged from the reactor. The degree of encrustation, measured as the weight per unit area of the encrustation, is then determined. The results are shown in Table 9.

Tabel Coating
liquid like
in vers. Example 10 9 Incrustation
(g / m ² ) Verse.
No. without Drying 430 62 * 14th __ 1 63 28 90 ⁰ C, 10 min 2 64 4th 3 00 65 * 10 Il 250 66 * Il

The inner walls of a 400 L charge stainless steel polymerization reactor with stirrer and the surface of the stirring tool are coated with a coating liquid coated, which contains 1 wt .-% solids and otherwise has the composition given in Table 10. the Coating is carried out in an amount that the dried

809831/06 41

"2901219

coating has a weight per unit area of 0.1 g / m ² . After the wet coating, it is dried in the manner shown in Table 9 and, after drying, washed with water.

The reactor prepared in this way is charged with 180 kg of deionized water, 74 kg of 1,3-butadiene monomer, 26 kg of acrylonitrile monomer, 4 kg of sodium oleate, 1 kg of oil acids, 500 g of tert-doaecyl mercaptan, 100 g of sodium diphosphate and 300 g of potassium peroxosulfate. The polymerization is carried out ^{at 40 °} C. for 12 h with stirring. After the polymerization reaction has ended and the reactor has been emptied, the weight per unit area of the polymer incrustation which has formed on the surfaces exposed to the monomer mixture is determined. The results are summarized in Table 10.

Coating
liquid like
in vers. Example 11 Tabel 10 Incrustation
(g / m ² ) Verse.
No. without Drying 330 67 * 14th 1 68 4th 90 ⁰ C, 10 min 280 69 * 10 Il 270 70 *

The experiments are carried out in an internally glazed polymerization reactor with a stirrer and a capacity of 400 liters

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carried out. The inner walls of the reactor and the stirrer surfaces exposed to the reaction mixture are coated with an aqueous coating liquid, the solids content of which is 1% by weight and the composition of which is shown in Table 11 in detail. The coating is applied in such an amount that the weight per unit area of the dried coating is 0.1 g / m ² . After the wet application, it is dried in the manner shown in Table 11 and finally washed with water. The polymerization reactor prepared in this way is charged with 180 kg of deionized water, 40 kg of 1,3-butadiene monomer, 54 kg of methyl methacrylate monomer, 4 kg of styrene monomer, 4.5 kg of sodium laurylbenzenesulfonate, 280 g of tert-dodecyl mercaptan and 300 g of potassium peroxosulfate. The polymerization is carried out ^{at 50 °} C. for 10 h with stirring. After the polymerization reaction has ended and the reaction mixture has been discharged from the reactor, the polymer incrustation on the surfaces is determined. The results are shown in Table 11.

Tabel Coating
liquid like
in vers. 11 Incrustation
(g / m ² ) Verse.
No. without
14th
4th Drying 130
0
100 71 *
72
73 * 90 ⁰ C, 10 min
Il

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280) 213

Example 12

The coating substances specified in Table 12, water-soluble anionic dyes are dissolved in water at a concentration of 1% by weight. The pH these solutions are then adjusted by adding the pH adjusting agents also given in Table 12. The monohydric alcohol indicated in Table 12 is then used in parts by weight there 100 parts by weight of aqueous solution specified amount added.

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 1,000 liters. The coating of the inner walls of the reactor and the surfaces of the stirring tool with the coating liquids mentioned is carried out in an amount such that the dried coating layer has a surface weight of 0.1 g / m ² . After the wet application, the coating is dried under the conditions given in Table 12 in each case.

The polymerization reactor prepared in this way is charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 250 g of partially saponified polyvinyl alcohol, 25 g of hydroxypropyl methyl cellulose and 75 g of diisopropyl peroxodicarbonate. The polymerization reaction is carried out ^{at 57 ° C. for 10 h with stirring.}

After completion of the polymerization reaction, the reactor is emptied and the polymer encrustation, which is attached to the has established surfaces exposed to the reaction mixture, examined for their basis weight. The results are compiled in Table 12.

In connection with the data shown in Table 12,

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Attention is drawn in particular to tests 87 and 88, from which it can be seen that the addition of methanol or ethanol with regard to the desired suppression of the formation of the polymer encrustation has a smaller effect than that have higher monohydric alcohols. In this connection, the comparative tests 89 and 90 also show that the addition surface-active substances instead of a monovalent alcohol significantly worsen the incrustation inhibition.

Table 12

Vers. Coating pH- pH-value alcohol dry encrustation no. Position- (weight- (g / m ² )

substance medium parts)

without

75 CI. Acid Sulfur- 6.0 Black 2 Acid

7 6 "" 6.0

C.I.Acid hydrochloric acid 6.5 Blue 158

C.I.Direct Molybdenum 4.5 Black 38 acid

C.I.Acid lactic acid 6.5 Blue 116

CI. Direct
Blue 106

C.I.Mordant Nitric 3.0 Violet 5 Acid

without -

without 90 ° C, 1 0 min

Isobutyl alcohol

n-butyl alcohol, 5

sec-butyl- 60 ⁰ C, alcohol, 10 30 me,

tert-butyl-50 ° C, alcohol, 10 60 min

tert-aryl "alcohol, 5

sec-amyl "alcohol, 10

1 15

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83 CI Direct
Violet 22 Phytm
acid 5.0 iso-butyl
alcohol, 5 60 °
30th C,
min 1 84 CIDirect
Violet 1 vinegar
acid 5.0 n-butyl
alcohol, 10 90 °
10 C,
min 7th 85 CIAcid
Violet 78 Glycolic
acid 5.5 tert-amyl
alcohol, 10 40 °
120 C.
min 1 36 CIMordant
Blue 1 phosphorus
acid 4.0 iso-butyl
alcohol, 10 dd 2 87 CIAcid
Black 2 sulfur
acid 6.0 Methanol, 10 90 °
10 C.
min 10 88 » It 6.0 Ethanol, 10 It 10 89 * Il ti 5.0 Hatriumlau-
ryl sulfate,
0.02 Il 300 90 * Il Il 5.0 Polyethylene
glycol loading
netzer, 1.0 It 500

Example 1 3

The aqueous coating liquids used in this example contain both anionic dyes (component a) and cationic dyes (component b). As explained at the outset, the names of the dyes are given according to the “Color Index”. The for the Components a and b respectively used substances and those for adjusting the pH of the aqueous coating liquid The pH adjusting agents used are listed in Table 13. The components are in a lot Dissolved in water that the total concentration of the three components, ie component a, component b and

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of the pH adjuster is about 0.1% by weight. The addition of the pH adjusting agent increases the pH the solution adjusted to the value also given in Table 1 3.

The experiments are carried out in a stainless steel polymerization reactor with a capacity of 100 liters. The coating liquid is applied in such an amount that the weight per unit area of the dried coating is not 0.1, as in the previous examples, but only 0.01 g / m ² . After wet application, the paint is dried under the conditions given in the table. In the polymerization reactor prepared in this way, suspension polymerization of vinyl chloride monomer is then carried out in the manner also described in Example 1. After the polymerization reaction has ended, the weight per unit area of the polymer incrustation found on the inner wall of the reactor is determined. The results are compiled in the table.

80933 1 / OSi 1

H5

- 4/1 -

280 1213

Tabel

Verse.
No.

component

Weight pH pH Dry Comp

Ratio A valuation crude

position

(a) / (b) medium (g / m ² )

91 * without

92 * Acid

Black 2

93 * without

94 Acid

Black 2

98 Acid

Blue 59

101 Acid
Orange 7

102 Acid
Blue 40

103 Acid
Blue 1

104 Direct
Blue 1

without without

Basic orange without

1,500

Basic blue

Basic Red 2

Basic blue

Basic orange

Basic yellow

Basic Blue 100/0 without 10.8 90 ⁰ C, 1,000

1 0min

0/100 without 5.0

100/20 P ₁

100/30 P ₁

100/40 P ₁

10 0/25 p

100/20
100/30

6.0 50 ⁰ C, 1 0m in 2.5 ti 2.5 Il 2.5 70 ⁰ C, 7min 5.0 50 ⁰ C, iOmin

2.5

2.0 70 ⁰ C, 7 min

2.5 50 ⁰ C, IOmin

3.0

1,000 10

100/15 P 2.0

100/20 P 2.5

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-γι -

28U \ l \%

105 Direct
Orange 26 basic
Red 1 100/40 ^P l 3.0 50 ⁰ C,
lOmin 1 106 Direct
Brown 37 basic
Blue 24 100/25 ^p i 2.5 Il 3 107 Direct
Green 26 basic
Blue 25 100/32 ^p i 2.0 11 2 108 Direct
Blue 71 basic
Violet 14 100/23 ^P 3 2.5 Il 1 109 Direct
Red 31 basic
Blue 9 100/27 ^P l 2.0 U 4th 110 Direct
Brown 1 basic
Green 5 100/18 ^p i 3.0 II 5

P ₁ = phytic acid

P ^ = disodium salt of phytic acid

P., = bis-triethanolamine salt of phytic acid

Example 1 4

An anionic dye (component a) and a cationic dye (b) are dissolved in water. The dyes are marked with their names according to the Color Index. The solution is given in Table 14 with the addition of pH adjusting agent adjusted to the pH value also given in Table 14. The total concentration of three components of the solution, i.e. component a, component b and the pH adjusting agent, is C, 1% by weight.

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 120 liters, The inner wall surfaces of the reactor and the stirring tool surfaces are coated with the aqueous coating liquid

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2801 * 19

wet coated in such a way that the dried coating layer has a weight per unit area of 0.01 g / m ² . After application, drying is carried out under the conditions given in Table 14. The dried coating is then washed with water.

The polymerization reactor treated in this way is charged with 50 kg of styrene monomer, 43.2 kg of deionized water, 120 g of hydroxyapatite, 0.62 g of sodium hydrogen sulfite, 125 g of benzoyl peroxide and 25 g of tert-butyl peroxobenzoate. It is polymerized with stirring to a temperature of 90 ^° C. for 7 hours. After the polymerization reaction has ended and the reaction mixture has been discharged from the reactor, the weight per unit area of the polymer incrustation which has formed in the reactor is determined. The results obtained are shown in Table 14.

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component a b 2 Tabel 14th pH
value Dry
tion Ver
crust verse
No. without without 3 Weight -
Relation PH-
A- (g / m ² ) acid
Black 2 without 11 (away) alternate
middle _ _ 280 Ill * Il basic
Blue 9 - - without 10.8 90 ⁰ C,
10min 220 112 * ti basic
Red 1 100/0 without 2.0 50 ⁰ C,
1 0min 0 113 Il basic
Blue 5 15th 100/20 ^P l 3.0 fl 2 114 It basic
Blue 6 100/40 ^P l 2.5 II 0 115 Il basic
Blue 12 100/50 ^p i 2.5 Il 1 116 Direct
Blue 86 basic
orange 100/30 ^p i 2.5 II 2 117 acid
Orange 3 Bas ic
Violet 100/45 ^p i 2.5 " 3 118 Direct
Black 19 basic
Yellow 100/23 ^P 4 2.0 70 ⁰ C,
5min 1 1 19th Direct
Blue 71 basic
Red 12 100/18 ^p i 2.0 It 0 120 acid
Blue 158 basic
Green 5 100/27 ^P l 2.5 It 3 121 Direct
Brown 1 basic
orange 100/30 ^p i 4.0 3 122 Direct
Green 1 basic
Blue 16 100/25 ^p i 2.5 40 ⁰ C,
15 minutes 0 123 100/20 ^P 5 4.0 ti 2 124 100/30 ^p i

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125 Direct Basic Green 26 Black 72

126 Acid Basic Red 80 Red 2

127 Acid Basic Red 52 Red 1

128 Acid Basic Yellow 7 Blue 25

129 Acid Basic

Orange 3 orange 14

100/34 ^P l 3.0 40 ⁰ C,
15 minutes Il 100/26 ^p i 2.5 50 ⁰ C,
1 Omin 100/23 ^p i 2.5 Il 100/40 ^p i 2.5 Il 100/20 P. 2.5

P ₁ = phytic acid

P. = diethylamine salt of phytic acid

P, = diammonium salt of phytic acid

Example 15

An anionic dye (component a), a cationic one Dye (component b), both named by Color Index, and a pH adjuster like them for each Case indicated in Table 15 are dissolved in water. The total concentration of the three components in the Solution is approximately 0.1% by weight. The pH of the solution is adjusted to the value also shown in Table 15. The adjustment is made by adding the specified pH adjusting agent.

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28UI219

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 4,00 l. The surfaces of the reactor and the stirrer which come into contact with the monomers are coated with the coating liquid in such a way that the dried coating has a surface weight of 0.01 g / m ² . After the wet coating, drying is carried out under the conditions given in Table 15. The coated surfaces are then washed with water.

The polymerization reactor prepared in this way is then charged with 80 kg of vinylidene chloride monomer, 20 kg of vinyl chloride monomer, 200 kg of deionized water, 150 g of benzoyl peroxide, 125 g of a partially saponified polyvinyl alcohol and 25 g of methyl cellulose. The polymerization reaction is carried out at a temperature of 60 ^{° C. for 12 h with stirring.} After the polymerization reaction has ended and the polymerization reaction mixture has been discharged, the weight per unit area of the polymer incrustation which has formed on the inner surfaces of the reactor and on the stirrer is determined. The results are shown in Table 15.

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component a b Table 15 100/30
14th pH
A- pH
value Dry
tion Ver
kru verse
No. without without Weight -
Relation 100/23
15th alternate
middle stung
(g / m ² ) acid
Black 2 without 100/33
6th without _ - 900 130 * acid
Blue 59 basic
Green _ - 100/24
2 without 1 0.8 90 ⁰ C,
lP-nin 800 131 * acid
Black 124 100/0 100/27 ^P l 3.0 If 1 132 Direct
Black 32 100/40
5 100/50
1 ^P l 2.0 If 0 133 Direct
Black 77 Basic 100/20
Blue 25 ^P 2 3.0 If 0 134 Direct
Orange 97 basic
orange ^P l 2.0 40 ⁰ C,
15 minutes 3 135 acid
Blue 113 basic
orange ^P l 2.5 Il 1 136 Direct
Brown 37 basic
Blue 1 ^P l 2.0 11 1 137 Direct
Blue 71 basic
orange ^p i 2.5 90 ⁰ C,
2min 0 138 basic
Red 12 ^P l 3.0 11 2 139 basic
Brown

= Phytic acid

"= Disodium salt of phytic acid

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Example 16

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 200. The surfaces of the reactor and the stirrer exposed to the monomer mixture are each coated with the coating liquid indicated in Table 16 in an amount such that the dried coating has a weight per unit area of 0.01 g / m ² . The solid concentration in the coating liquid is 0.1% by weight. After the wet application of the aqueous coating solution, drying is carried out under the conditions given in Table 16. The surfaces coated in this way are then washed with water.

The polymerization reactor treated in this way is then coated with 50 kg of styrene monomer, 50 kg of deionized water, 125 g of partially saponified polyvinyl alcohol, 25 g of methylcellulose and 150 g of benzoyl peroxide. The polymerization reaction is carried out at a temperature of 90 ^{° C. for 7 h with stirring.} After the polymerization reaction has ended, the reaction mixture is discharged and the weight per unit area of the polymer incrustation that has formed inside the polymerization reactor is determined. The results obtained are shown in Table 16.

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26Ü1219

Coating
liquid like
in vers. Table 1 6th - 10min Incrustation
(g / m ² ) Verse.
No. without Drying 1 0min 800 140 * 4th - 600 141 * 96 90 ⁰ C, 0 142 99 50 ⁰ C, 1 143 104 Il 10min 2 144 108 Il 7min 5 145 113 H 15 minutes 0 146 120 60 ° C, 1 0min 0 147 124 70 ⁰ C, 0 148 129 40 ⁰ C, 15 minutes 2 149 134 5O ⁰ C, 3 150 137 Il 1 151 40 ⁰ C,

Example 17

The experiments are carried out in a stainless steel polymerization reactor equipped with a stirrer and has a capacity of 250 liters. The surfaces of the reactor exposed to the monomer mix and the stirrer are coated with an aqueous coating liquid coated having the composition shown in Table 17 and a total solid concentration

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5 »

-SO-

280 1213

of 0.1% by weight. The coating is carried out in such a way that the dried coating has a weight per unit area of 0.01 g / m ² . After the wet coating, the paint is dried under the drying conditions given in Table 17 and then washed with water.

The polymerization reactor prepared in this way is then coated with 60 kg of styrene monomer, 40 kg of acrylonitrile monomer, 100 kg of deionized water, 2 kg of hydroxyapatite, 40 g of sodium lauryl sulfate, 300 g of tert-dodecyl mercaptan and 400 g of lauroyl peroxide. The polymerization reaction is carried out with a gradual increase in the temperature of the polymerization reaction mixture, namely first 1 h at 70 ^° C. / then 2 h at 70 to 80 ^° C. and finally 1 h at 80 ^° C. Under these conditions, a styrene-acrylonitrile Copolymer of the highest quality obtained. After the reactor has been emptied, the weight per unit area of the polymer incrustation is determined which has formed on the surfaces of the reactor and the stirrer exposed to the reaction mixture. The results obtained are shown in Table 17.

Coating
liquid like
in vers. Table 17 10min Incrustation
(g / m ² ) Verse.
No. without 10min 1,000 152 * 4th Drying 800 153 * 99 - 0 154 105 9O ⁰ C, 1 0min 3 155 107 50 ⁰ C, 5 156 113 II 0 157 Il 60 ⁰ C,

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158 134 50 ⁰ C, 10 min 0

159 137 "2

Example 18

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 1,000. The surfaces of the reactor and the stirrer exposed to the monomer mixture are coated with the aqueous coating liquid indicated in Table 18 for each individual experiment. The coating liquid has a total concentration of the dissolved components of 0.1% by weight and is applied to the surfaces to be protected in such a way that the dried coating has a weight per unit area of 0.01 g / m ² . After the wet application, the paint is dried under the action of heat under the conditions detailed in Table 18. The dried coating is then washed thoroughly with water.

The polymerization reactor prepared in this way is then charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water, 250 g of hydroxypropylmethylcellulose, 250 g of sorbitan monolaurate and 50 g of α, α'-azobis-2,4-dimethylvaleronitrile. The polymerization reaction is then carried out ^{at 57 ° C. for 12 h with stirring.}

After the completion of the polymerization reaction, the polymerization reaction mixture becomes discharged from the reactor. The emptied reactor is then washed with water. Then a new polymerization batch of the same type is run in the same reactor without the protective surfaces can be coated again. The polymerization in the new approach will be among the same

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- 52 -

Conditions such as the polymerization carried out in the first batch. This procedure is repeated until the polymer encrustation forming on the surfaces exposed to the reaction mixture has reached ^{a weight per unit area of 1 g / m 2.} The number of polymerizations which can be carried out up to this limit value is given in Table 18.

Table 18

Verse.
No. Coating
liquid like
in vers. Drying Number of poly
merization
sentences 160 * without - 0 161 * 4th 9O ⁰ C, 10 min 0 162 95 20 ⁰ C, 10 min 30th 163 96 Il 40 164 99 Il 20th 165 104 Il 14th 166 113 Il 26th

Example 19

The procedure described in Example 13 is carried out under the conditions specified there repeated with the modification that the coating liquids additionally with a monohydric alcohol are added. The kind and the amount of the monohydric alcohol added to each of the coating liquid are shown in Table 19. the

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2801213

Wet-coated surfaces to be protected are dried ^{at 50 ° C. for 10 minutes with heating.}

The results obtained are indicated by the weight per unit area of the incrustation observed in each case on the Surfaces exposed to the reaction mixture are compiled in the table.

By adding the monohydric alcohol to the coating liquid the application of the aqueous coating liquid, in particular its spreading on the stainless steel surfaces relieved. There are more closed wet coatings and, accordingly, more closed dried coatings obtain.

Table 19

Vers. Coating liquid incrustation

No. (as in version No., additional alcohol) (g / m ² )

167 94 and 10% by weight isobutyl alcohol 7

168 101 and 5% by weight sec-butyl alcohol 0

169 103 and 10% by weight tert-butyl alcohol 2

170 106 and 10% by weight tert-amyl alcohol 0

171 110 and 10% by weight sec-amyl alcohol 3

Example 20

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 100 carried out. The surfaces of the reactor and the stirrer exposed to the reaction mixture are coated in such a way that the basis weight of the dried

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"- 280 1218

Coating is 0.1 g / m ² . The coating liquid is prepared by dissolving the anionic dye given in Table 20 (component a) and the metal salt given in Table 20 (component c) with subsequent addition of the pH adjusting agent and setting the pH value given in Table 20. The anionic dye (component a) is indicated by its name according to the color index. The weight ratio in which components a and c are present to one another is given in Table 20. The total concentration of components a and c in the liquid is 1% by weight. The pH is adjusted by adding hydrochloric acid as a pH adjusting agent. After the coating liquid has been applied, the coating is dried under the conditions shown in Table 20. The dried coating is then washed thoroughly with water.

The polymerization reactor prepared in this way is charged with 26 kg of vinyl chloride monomer, 52 kg of deionized water, 26 g of partially saponified polyvinyl alcohol and 8 g of α, α'-azobis-2,4-dimethylvaleronitrile. The polymerization reaction is then carried out at 57 ^° C. for 8 h with stirring. After the polymerization reaction has ended, the reactor is emptied and the weight per unit area of the polymer incrustation which has formed on the surfaces exposed to the reaction mixture is determined. The results are shown in Table 20.

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5 <\

- 56 -

Table 20

Verse
No. component a C. Weight -
Relation PH-
value Drying incrustation 1 (g / m ² ) without without (a) / (c) , lOmin 1 500 201 * acid
Black 2 without - - - 000 202 * 11 Sodium-
silicate 100/0 10.8 90 ⁰ C 12th 203 ir It 100/100 6.0 Il 0 204 ■ 1 11 100/100 5.0 If 1 205 Mordant
Violet 5 Potassium-
silicate 100/100 3.0 It 3 206 Direct
Blue 71 Sodium-
silicate 100/50 5.0 Il C, 30min 2 207 acid
Black 1 ti 100/100 5.0 It C, 5min 0 208 Direct
Black. 1 ti 100/100 5.0 80 ° 1 209 Mordant
Black 5 Il 100/25 4.5 90 ° 0 210 Direct
Red 1 it 25/100 3.5 ti 2 211 ti ti 100/20 5.0 It C, 10min 900 212 * ■■ FeCl ₂ 0/100 10.0 Il 1150 213 * It FeCl ₃ 0/100 3.0 90 ° 1200 214 * acid
Black 2 FeCl ₂ 0/100 5.0 Il C, 10min 0 215 acid
Black 2 CaCl ₂ 100/13 5.0 Il C, 120 min 0 216 Direct
Blue 6 Copper (I.
acetate 100/8 5.0 90 ° 1 217 I) - 100/7 5.0 40 °

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218 Mordant iron (II) -blue 1 nitrate

219 Direct ZnCl Orange 10

220 Acid ^FeC1 2 Yellow 38

221 Acid FeCl / Black 2 zinc acetate

(1: 4)

100/13 3.0 90 ° C, 10rain 1 100/7 5.0

100/7 4.0 90 ° C, 5min 100/3 5.0 90 ° C, 10min 0

Example 21

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 1000 liters. The coating liquid with which the surfaces exposed to the polymerization reaction mixture are protected has a concentration of 1% by weight. The composition of the aqueous coating liquid is shown in Table 21 for each of the experiments. The surfaces are coated with the coating liquid in such a way that the dried coating has a weight per unit area of 0.1 g / m ² . After the application of the coating liquid, the coating is dried under the conditions shown in Table 21.

The polymerization reactor pretreated in this way is then charged with 200 kg of vinyl chloride monomer, 400 kg of deionized water and the other substances detailed in Table 21. The polymerization is carried out ^{at 57 °} C. for 10 h with stirring. After the polymerization reaction has ended and the polymerization reaction mixture has been discharged from the reactor, the weight per unit area of the encrustation observed is determined. The results obtained are shown in Table 21.

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The tests Nos. 223 and 224 included in Table 21 differ from the other tests of this one For example, no homopolymers, but rather serve to demonstrate the effectiveness of the invention in the copolymerization as well of vinyl chloride with vinyl acetate. In Experiment No. 223, the starting mixture contains 200 kg of vinyl chloride in addition to an additional 10 kg of vinyl acetate and, in Experiment 224, in addition to the 200 kg of vinyl chloride, an additional 37.5 kg of vinyl acetate.

Table 21

verse
IJr. .Coating
liquid
as in verse.
No. Dry
tion initiator
(kg) Disperser
(kg) Additive
(kg) Ver
kru
stung
(G/
m ») 0 222 204 60 ⁰ C,
120min UMVN,
0.05 HPMC, 0.2 5
+ SML, 0.25 without 0 223 205 70 ⁰ C,
60min Il PVA, 0.2 5 without 0 224 208 80 ⁰ C,
30 min Il without 0 225 210 90 ⁰ C,
5min LPO,
1.3 If stearin
acid,
0.25 -0 226 220 Il DMVN,
0.075 PVA, 0.25 without 0 227 216 Il DMVN
0.05 HPMC, 0.25
+ SML, 0.25 without 0 228 219 Il LPO,
1.3 PVA, 0.25 Stearin-0
acid,
0.25 229 221 Il IPP
0.05 PVA, 0.25
+ Methyl
cellulose,
0.05 (**)

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230 * 213 90 ⁰ C, DMVN, PVA, 0.25 without 1200 10min 0.075 231 * 213 II KPS, Na-LS, without 1500 ο, 13 2.5

(**) Potassium stearate, 2.5 + rice wax 3.0 +

Dioctyltin mercaptide, 1.75 + polyethylene wax,

DMVN = α, a'-azobis-2,4-dimethylvaleronitrile LPO = lauroyl peroxide

IPP = diisopropyl peroxodicarbonate KPS = potassium peroxosulfate

HPMC = hydroxypropylmethyl cellulose SML = sorbitan monolaurate

PVA = partially saponified polyvinyl alcohol Na-LS = sodium lauryl sulfate

Example 22

The tests are carried out in a combined system in which a standing 21 reactor and a horizontally lying 41 reactor, both made of stainless steel, are connected to one another. The inner walls and all parts of this system which come into contact with the monomers are coated with an aqueous coating liquid which, at a concentration of 1% by weight, has the composition given in the table and is applied in an amount that the dried coating has a weight per unit area of 0.1 g / m ² . After the wet application of the respective coating liquid, drying is carried out under the conditions given in Table 22. The dried coating is then washed with water and

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28ÜI213

post-dried.

The upright 21 reactor prepared in this way is loaded with 800 g
Vinyl chloride monomer and 0.3 g of diisopropyl peroxodicarbonate are charged. Polymerization is carried out at 60 ^° C. for 2 h with stirring. The speed of the stirrer is 900 min. Afterward
the polymerization reaction mixture is transferred to the horizontal 41 reactor, in the 800 g of vinyl chloride monomer
and 0.4 g of diisopropyl peroxodicarbonate are presented. The polymerization reaction is continued again at 57 ^° C. for 10 h with stirring. The speed of the stirrer in the 41 reactor is 100 min. After the polymerisation reaction has ended, the reaction mixture is discharged from the reactor and becomes the weight per unit area of the polymer encrustations
determined in each of the two reactors. The results obtained are summarized in Table 22.

Table 22

Verse.
No. Coating
fluid flow Drying Incrustation (g / m ² ) 41 reactor sness like
in vers. 21 reactor 800 232 * without __ 900 700 233 * 4th 90 ⁰ C, 10 min 700 0 234 204 7 0 ° C, 60mir. 2 0 235 215 90 ⁰ C, 10 min 1 1 236 221 9O ⁰ C, 5min 2

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- βο

Example 23

The experiments are carried out in an internally glazed polymerization reactor with a stirrer and a capacity of 100 liters. The coating solution, the composition of which is given in detail in Table 23, has a concentration of 1% by weight and is applied to the surfaces to be protected in an amount such that the dried coating has a weight per unit area of 0.1 g / m ² having. After the wet application of the coating liquid, the wet coating is dried under the action of heat under the conditions shown in Table 23. The dried coating is washed thoroughly with water.

The polymerization reactor prepared in this way is charged with 20 kg of vinyl chloride monomer, 40 kg of deionized water, 13 g of potassium peroxosulfate and 250 g of sodium lauryl sulfate. The polymerization reaction is then carried out ^{at 50 ° C. for 12 h with stirring.} After the polymerization reaction has ended, the reaction mixture is discharged from the reactor and the weight per unit area of the incrustation that has formed on the reactor walls is determined. The results obtained are shown in Table 23.

Coating Table 23 Incrustation Verse. flow Drying siykeit like in version no. (g / m ² ) without 700 237 * 4th - 400 238 * 206 90 ⁰ C, 10 min 0 239 210 Il 0 240 221 Il 0 241

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Example 24

The experiments are carried out in a stainless steel polymerisation reactor with a stirrer and a capacity of 100 liters. The surfaces of the reactor, the stirrer and the other parts of the plant exposed to the feed are heated to the temperature given in Table 24 before being coated with the coating liquid. At this temperature, the coating liquid is then applied to the surfaces to be protected. The 1% by weight aqueous coating liquid, which has the composition shown in Table 24, is applied in an amount such that the dried coating has a basis weight of 0.1 g / m ² . The dried coating is then washed directly with water.

In the reactor prepared in this way, vinyl chloride is then polymerized, namely among the essentially the same conditions as given in Example 20. After completion of the polymerization reaction and discharge of the In the reaction mixture, the weight per unit area of the polymer incrustation is determined, which is on the reactor walls has formed. The results are shown in detail in Table 24.

Table 24

Vers. Coating liquid wall and stirrer incrustation no. As in vers. temperature (g / m ² )

242 * without - 1 500 243 * 4th 90 ⁰ C 1 000 244 204 80 ⁰ C 0 245 216 50 ⁰ C 2 246 210 40 ⁰ C 5 247 221 90 ⁰ C 0

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Example 25

The experiments are carried out in a polymerization reactor with a stirrer and a capacity of 400 liters. All parts of the system are made of stainless steel. The surfaces of the installation exposed to the monomer mixture are coated with an aqueous coating liquid which, at a concentration of 1% by weight, has the composition given in Table 25. The coating liquid is applied in such an amount that the dried coating has a weight per unit area of 0.1 g / m ² . After the liquid has been applied, the wet coating is dried under the conditions given in Table 25. The dried coating is then washed with water.

The thus prepared polymerization reactor is charged with 200 kg of deionized water ", 100 kg of styrene monomer, 1 kg of calcium phosphate, charged 10 g of sodium dodecylbenzenesulfonate and 100 g of benzoyl peroxide. The polymerization reaction is then carried out with stirring 11h under heating at 90 ⁰ C, After completion of the polymerization reaction is the The reactor is emptied and the weight per unit area of the polymer incrustation is determined, which has settled on the reactor walls. The results are shown in Table 25.

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Table 25

Vers. Coating liquid drying incrustation no. Liquid as in

Vers.No. {g / m ² )

248 * without - 280 249 * 10 90 ⁰ C, 10 min 200 250 204 Il 0 251 205 0 252 208 80 ° C, 30 min 0 253 215 90 ⁰ C, 10 min 0 254 210 Il 0 255 221 Il 0 Example 26

The experiments are carried out in the same polymerization reactor in which the experiments described in Example 25 were carried out. The reactor surfaces and stirrer surfaces which come into contact with the monomers are coated with an aqueous coating liquid which has the composition shown in Table 26 at a concentration of 1% by weight. The coating liquid is applied in such an amount that the dried coating has a basis weight of 0.1 g / m ² . After the application of the coating liquid, the wet coating is dried under the conditions shown in Table 26. It is then washed with water.

809831/0641

The polymerization is then carried out in the manner described in Example 25 in the polymerization reactor prepared in this way. After the completion of the polymerization reaction, the polymerization reaction mixture is discharged from the reactor. The reactor is then washed out with water, charged again in the same way and a new polymerization batch is run under the same conditions as before. This process is repeated until the polymer incrustation gradually forming on the reactor walls has reached ^{a weight per unit area of 1 g / m 2.} The number of polymerization batches that can be carried out in this way without renewing the coating is listed in Table 26.

Table 26

Vers. Coating liquid no. as in vers.

Drying Number of polymerization batches

256 * without - 0 257 * 4th 90 ⁰ C, 10 min 0 25 8 204 It 16 259 216 Il 34 260 221 It 40 Example 27

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 400 liters. The system surfaces that come into contact with the monomer mixture are coated with a coating liquid in an amount sufficient to dry

809831/0641

-re- 28D12I3

Obtain coating with a basis weight of 0.1 g / m ² . The aqueous coating liquid used for this purpose has the composition given in the table at a concentration of 1% by weight. With the action of heat, drying is then carried out under the conditions given in Table 27. The dried coating is then washed thoroughly with water.

The polymerization reactor prepared in this way is then charged with 180 kg of deionized water, 75 kg of 1,3-butadiene monomer, 25 kg of styrene monomer, 4.5 kg of sodium lauryl sulfate, 280 g of tert-dodecyl mercaptan and 300 g of potassium peroxosulfate. The polymerization is then carried out at a temperature of 50 ^{° C. for 12 h with stirring.} After the polymerization reaction has ended and the polymerization reaction mixture has been discharged from the reactor, the weight per unit area of the polymer incrustation which has settled on the reactor walls is determined. The results are summarized in Table 27.

Table 27

Vers. Coating liquid drying incrustation no. As in vers. No. (g / m ² )

430

9O ⁰ C, 10min 300

261 * without 262 * 4th 263 205 264 215 265 221

809831/06

Example 28

Experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 400 liters. The system surfaces exposed to the monomer mixture are coated with the coating solution specified in Table 28, which has a concentration of 1% by weight, in an amount such that the coating obtained after drying has a weight per unit area of 0.1 g / has m ² . After the application of the coating liquid, the wet coating is dried under the influence of heat under the conditions shown in Table 28 and then washed with water.

The polymerization reactor prepared in this way is then charged with 180 kg of deionized water, 74 kg of 1,3-butadiene monomer, 26 kg of acrylonitrile monomer, 4 kg of sodium oleate, 1 kg of oleic acid, 50 g of tert-dodecyl mercaptan, ¹ Og of sodium diphosphate and 300 g of potassium peroxosulfate The polymerization is then carried out with stirring for 12 hours at a temperature of 40 ^° C. After the polymerization reaction has ended and the polymerization reaction mixture has been discharged, the weight per unit area of the polymer incrustation that has formed on the system walls is determined.

Table 28

Verse.
No. Coating liquid
as in vers. 809831 Drying / 0641 Incrustation
(g / m ² ) 266 * without - 330 267 * 4th 90 ⁰ C, 10 min 280 268 205 It 0 269 221 0

280 1218

Example 29

The experiments are carried out in an internally glazed polymerization reactor with a stirrer and a capacity of 400 liters. The surfaces of the reactor wall and of the stirrer which come into contact with the reaction mixture are coated with a coating liquid in an amount such that the dried coating has a weight per unit area of 0.1 g / m ² . The aqueous coating liquid has a concentration of 1% by weight and otherwise has the composition given in Table 29 for each individual book. After applying the aqueous coating liquid and drying the wet coating under the conditions shown in Table 29, the coated surfaces are thoroughly washed with water. The polymerization reactor prepared in this way is then charged with 180 kg of deionized water, 40 kg of 1,3-butadiene monomer, 54 kg of methyl methacrylate monomer, 4 kg of styrene monomer, 4.5 kg of sodium laurylbenzenesulfonate, 280 g of tert-dodecyl mercaptan and 300 g of potassium peroxosulfate. The polymerization is then carried out at a temperature of 50 ^{° C. for 10 h with stirring.} After the polymerization reaction is complete and the polymerization reaction mixture is discharged from the reactor, the reactor is thoroughly washed out with water. The weight per unit area of the polymer incrustation that has adhered to the reactor walls is then determined. The results obtained are summarized in Table 29.

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Tabel Example 30 29 Drying Incrustation
(g / m ² ) Verse.
No. Coating liquid
as in vers. 90 ⁰ C, 10 min
Il
Il 130
100
0
0 270 *
271 *
272
273 without
4th
205
221

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 200 liters. The surfaces of the system which come into contact with the reaction mixture are coated with the coating liquid mentioned in Table 30, which has a concentration of 1% by weight. The coating liquid is applied in an amount sufficient to give the dried coating a basis weight of 0.1 g / m ² . The composition of the coating liquid is shown in Table 30. After the application of the coating liquid, the wet coating is dried under the conditions shown in Table 30 with heating. The dried coatings are then washed with water.

The polymerization reactor prepared in this way is then filled with 30 kg of polybutadiene latex with a solids content of 50% by weight, 50 kg of styrene monomer, 20 kg of acrylonitrile monomer, 100 g of tert-dodecyl mercaptan, 500 g of potassium oleate and 500 g Charged with potassium peroxosulfate. Then, while stirring

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280 1213

Polymerized at 50 ^° C. for 15 h. The ABS resin emulsion obtained is discharged from the reactor after the reaction has ended. The weight per unit area of the polymer incrustation that has formed on the system walls is determined. The results are summarized in Table 30.

Table 30 Drying Incrustation
(g / n ² ) Verse.
No. Coating liquid
as in vers. - 180 274 * without 90 ⁰ C, 10 min 180 275 * 4th Il 130 276 * 212 Il 0 277 205 Il 0 278 221

Example 3 1

For the preparation of the aqueous coating liquid are an anionic dye (component a), which is characterized by its name according to the Color Index, and a metal salt (component c) dissolved in water in a total concentration of 1% by weight. The components are for everyone Test given in Table 31. After preparing the solution, the pH is adjusted by adding hydrochloric acid pH adjusting agent adjusted to the pH value also given in table 31. It also comes with the solution a monohydric alcohol in an amount of 10 parts by weight, based on 100 parts by weight of the aqueous solution of the dye and the metal salt, the type of alcohol added being shown in Table 31.

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280 1213

The experiments are carried out in a stainless steel polymerization reactor with a stirrer and a capacity of 100 liters. The system parts which come into contact with the monomer mixture are coated with the above-mentioned coating liquid. The coating is carried out in such a way that the dried coating has a weight per unit area of 0.1 g / m ² . The wet coating is dried under the conditions given in Table 31. After drying, the coated surfaces are washed with water.

The polymerization reactor treated in this way is charged with 26 kg of vinyl chloride monomer, 52 kg of deionized water, 26 g of partially saponified polyvinyl alcohol and 8 g of α, α'-azobis-2,4-dimethylvaleronitrile. The polymerization reaction is carried out ^{at 57 ° C. for 8 h with stirring.} After completion of the polymerization reaction and discharge of the reaction mixture from the reactor, the weight per unit area of the polymer incrustation is determined, which is based on the. Reaction mixture has set exposed system surfaces. The results are shown in Table 31.

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-I ⁵ -

component a C. Table 31 pH alcohol dry
Value recovery - without = tert-Amy! alcohol - Ver
kru verse
No. without without Weight ratio ,8th without 90 ⁰ C,
1 0min stung
ig / no) acid
Black 2 without (a) / (C) , 0 ^A l 1 5 C C 279 * ti sodium
silicate - 10 -0 ^A 2 ti ι o: o 230 * It ti 100/0 3, , 0 ^A l 70 ⁰ C,
60min 0 231 Direct
Yellow I 11 100/100 6, , 0 ^A l 90 ⁰ C,
1 0min 1 282 Mordant
Violet 5 potassium
silicate 100/20 5, , 0 ^A i II 0 283 Direct
Blue 71 sodium
silicate 100/50 5, , 5 ^A 3 90 ⁰ C,
5min ^c ' 284 Mordant
Black 5 ti 100/50 5, , 0 ^A 3 It 235 acid
Blue 116 ti 100/100 3, , 0 ^A 4 ti - 236 Direct
Red 1 ti 25/100 5. , 0 ^A 4 9O ⁰ C,
1 0min 1 2S7 acid
Black 2 FeCl ₂ 15/100 6, , 0 ^A 4 Il 1 233 ti FeCl 100/20 5, , 0 ^A l Il 289 Il zinc
acetate 100/13 5 = Isobutyl alcohol C. 2 90 ^A 1 100/13 6th = sec-butyl alcohol 1 291 100/13 = sec-amyl alcohol ^A 3 ^A 4

809831/0641

Example 32

The experiments are carried out in a stainless steel polymerization reactor which is equipped with a stirrer and has a capacity of 50 liters. The surfaces of the system, including the stirrer, exposed to the monomer mixture are coated with a coating liquid which has the composition shown in Table 32 at a concentration of 1% by weight. After the application of the coating liquid, the wet coating is dried under the conditions shown in Table 32 with the supply of heat. The dried coating has a weight per unit area of 0.1 g / m ² . The coating is washed with water after drying. The polymerization reactor prepared in this way is charged with 20 kg of deionized water, 10 kg of styrene monomer, 100 g of calcium phosphate, 10 g of sodium dodecylbenzenesulfonate and 10 g of benzoyl peroxide. The mixture is then polymerized with stirring 11h at 90 ⁰ C. After the polymerization reaction has ended, the polymerization mixture is discharged from the reactor. The reactor is then washed thoroughly with water. The reactor is then charged again in the same way and a new polymerization batch is run. This process is repeated until the polymer encrustation adhering to the walls of the system exposed to the reaction mixture has a weight per unit area of 1 g / m ² . The number of polymerization batches to be carried out in this way without renewing the coating of the walls to be protected is determined. The results are summarized in Table 32.

809831/0641

Sightseeing Table 32 7er s. liquid like Drying No. in version number, without 2 92 * 4th - 293 * 282 ηη ° c λ Ar »: ·;
J 'J V- * * "IU ^. 294 281 U 295 285 296 289 I! 297 I!

■ • zeAii. aar poly

809831/0641

Claims (1)

JAEGKH, GRAMS & PONTANI 1'ATHNTANWaIVI ¹ H 28 Ω 1 2 C =; -. C ^ E.y. DR. KLAUS JAEGER DIPL.-ING. KLAUS D. GRAMS DR.-ING. HANS H. C-I- £ 3-JTiNG ■ BERGSTR. · Ί8 '/> fcO31 STOCKDORF- KFiEUZWEG 34 S7S2 KLEINOiÄTHEiM ■ HI-iiCn = F « Sr.ir.-Etsu Chemical Co., Ltd. SHI-18 6-1, Ote ::; ächi 2-chome, Chiyoda-ku, Tokyo, Japan Process for polymerizing vinyl monomers Claims \ y Process for the polymerisation of vinyl monomers, in which the polymerisation is carried out in a polymerisation reactor whose surfaces which come into contact with the vinyl monomers are wet coated with one or a mixture of several polar organic substances from the charging of the reactor with the starting component mixture to be polymerised and then dried characterized in that the polymerization is carried out in a polymerization reactor in which the surfaces that come into contact with the polymerization starting component mixture are coated with an aqueous coating liquid containing at least one alkali metal salt or an ammonium salt of a water-soluble anionic dye. Contains sulfonic acid type and / or carboxylic acid type and is adjusted to a pH of not greater than 7 with the addition of a pII-adjusting agent. 809831/0641 2. The method according to claim 1, characterized in that the aqueous coating liquid additionally contains a monohydric alcohol having 3 to 5 carbon atoms in the molecule at a concentration of 1 to 20% by weight based on the weight of the coating liquid contains. 3. The method according to any one of claims 1 or 2, characterized in that the concentration of the alkali metal salt and / or ammonium salt of the water-soluble anionic dye in the aqueous Coating liquid is in the range of 0.01 to 5% by weight. 4. The method according to any one of claims 1 to 3, characterized in that the pH value of the aqueous coating liquid is set to a value less than or equal to 5. 5. The method according to any one of claims 1 to 4, characterized in that the first wet coating applied under heat at a temperature in the range of 40 to 100 ⁰ C is dried. 6. The method according to any one of claims 1 to 5, characterized in that the wet coating is carried out in such a way that the dried coating resulting therefrom has a weight per unit area of at least 0.001 g / m ² . 7. The method according to any one of claims 1 to 6, characterized in that as a pH adjusting agent one of the following substances is used: sulfuric acid, phosphoric acid, nitric acid, molybdic acid, Lactic acid, glycolic acid, thioglycolic acid, phytic acid or, if they are formed, their acid salts. 8. The method according to any one of claims 1 to 7, characterized in that the coating liquid in addition to the salt of the anionic dye (component a) as component b a water-soluble one cationic dye having at least one pair of conjugated double bonds and preferably at least contains a nitrogen atom in the molecule. 9. The method according to claim 8, characterized in that the weight ratio of component b for component a is in the range from 100: 0.1 to 100: 1000. 809831/0641 ~ ⁴ '28Q1219 0O. Method according to one of Claims 8 or 9, characterized in that the pH adjusting means Are phytic acid or its acidic salts. 11. The method according to any one of claims 1 to 10, characterized in that the aqueous Coating liquid in addition to component a or to components a and b as component c at least contains one of the following substances: silicas, silicates and water-soluble metal salts, if these are not alkali metal salts. 12. The method according to claim 11, marked in that the weight ratio of component c or, in the presence of component b, the weight ratio of components b and c together to component a is in the range from 100: 0.1 to 100: 1000. 0 9 8 31/0641